Process for printing textile fibre materials in accordance with the ink-jet printing process

ABSTRACT

An ink-jet printing process for printing textile fibre materials, wherein the fiber materials are printed with an aqueous ink comprising (I) at least one fiber reactive dye, and (II) a di, tri or tetramer of a C 2 -C 4 oxyalkylene or a mono- or di-C 1 -C 4 -alkyl ether of a di, tri or tetramer of a C 2 -C 4 -oxyalkylene, said ink having a viscosity from 5 to 20 mPas at 25° C., and wherein the said ink is applied to the fiber material with an ink-jet print head comprising an ink supply layer (b) receiving ink from an external ink reservoir, said ink supply layer having a first side and a second side and comprising, a porous medium having a plurality of pores therein and a plurality of holes extending therethrough, so as to allow passage of the ink allows for high speed printing and yields prints with good fastness properties.

The present invention relates to a process for printing textile fibrematerials using reactive dyes in accordance with the inkjet printingprocess and to corresponding printing inks.

Rotary and flat-screen printing are presently prevailing as textileprinting methods. However, these conventional methods are not profitableunless the quantity of the product is sufficiently large. In addition,since the fashion of the print pattern changes rapidly, there is a riskin that a large quantity of the printed products are not sold but keptin stock when production cannot follow the rapid change in the fashion.Accordingly, there is a demand for establishing electronic textileprinting systems, such as inkjet, that require no printing plates andare suited for multi-item and small-quantity production and respond tofashion rapidly.

Ink-jet printing technology opens up new design capabilities aroundcolors, patterns and images. The ability to change colors and designsquickly is one of the major advantages of ink-jet printing over rotarytraditional screen-printing methods. In a digital system, design changesare enabled through software, without needing to engrave screens. Colorchanges are also made at the computer, eliminating the process ofcleaning screens and changing inks. Actual fabric samples of new designsare possible at a fraction of the cost and in a fraction of the timeformerly needed. By this way designers and textile and apparel companiescan interact to bring new products to market almost instantaneously.Instantaneous data transfer over the global Internet and similar dataexchange via local area networks (LANs) make it possible to exchangeideas faster than ever.

Despite the many advantages, inkjet still suffers from some drawbacks,some of which become even more pronounced when print speed isincreasing. Hardware reliability (e.g. clogged nozzles) and speedlimitations are technical barriers limiting the use of ink-jet printingprimarily to generation of samples. State of the art inkjet textileprinters are capable of printing 2 to 30 m²/h operating at a frequencyof 2 to 8 KHz. In order to become a true production method both forshort runs and for sampling, ink-jet processes are required which arereliable even at high print speed (e.g. 150 m²/h). However, whenprinting at high speed, the response to high frequency is liable to beimpaired and the ink tends to be unstable depending on the physicalproperty of the ink, owing to the fact that the ink has to be dischargedthrough minute nozzles at high velocity and at high frequency.Furthermore, the quality of the print tends to be impaired due toblotting on the both, partly because the ink jet printer does not allowthe use of an ink having high viscosity and partly because both usuallyhas rougher texture than paper, thus making it difficult to printpatterns of minute or delicate design.

Accordingly there is a need for inkjet printing processes which can beconducted with high reliability, even when running at a high printspeed, with an appreciable resolution and which have optimumcharacteristics from the standpoint of application technology. In thisconnection the properties of the inks used, such as the viscosity,stability, surface-tension and conductivity, play a decisive role.Furthermore, high demands are being made in terms of the quality of theresulting prints, e.g. in respect of colour strength, fibre-dye bondstability and fastness to wetting. Those demands are not met by theknown processes in all characteristics, so that there is still a needfor new processes for the ink-jet printing of textiles.

The invention relates to an inkjet printing process for printing textilefibre materials, wherein the fiber materials are printed with an aqueousink comprising

(I) at least one fiber reactive dye, and

(II) a di, tri or tetramer of a C₂-C₄-oxyalkylene or a mono- ordi-C₁-C₄-alkyl ether of a di, tri or tetramer of a C₂-C₄-oxyalkylene,

said ink having a viscosity from 5 to 20 mPa s at 25° C, and wherein

said ink is applied to the fiber material with an ink-jet print headcomprising

an ink supply layer (b) receiving ink from an external ink reservoir,said ink supply layer having a first side and a second side andcomprising, a porous medium having a plurality of pores therein and aplurality of holes extending therethrough, so as to allow passage of theink.

The dyes used in the inks should preferably have a low salt content,that is to say they should have a total content of salts of less than0.5% by weight, based on the weight of the dyes. Dyes that haverelatively high salt contents as a result of their preparation and/or asa result of the subsequent addition of diluents can be desalted, forexample, by membrane separation procedures, such as ultrafiltration,reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% byweight, preferably from 1 to 30% by weight, especially from 1 to 20% byweight and more especially from 1 to 15% by weight based on the totalweight of the ink. As a lower limit, a limit of 1.5% by weight,preferably 2% by weight and especially 3% by weight, is preferred.

As the fiber reactive dyes there come into consideration, for example,dyes of the formulaA₁-(Z₁)₁₋₃   (1).

wherein

A₁ is the radical of a monoazo, disazo, polyazo, metal-complexed azo,anthraquinone, phthalocyanine, formazan or dioxazine chromophore havingat least one sulfo group, and

(Z₁)₁₋₃ is 1 to 3 identical or different fiber reactive radicals, ordyes of the formula

wherein

Q₁, Q₂, Q₃ and Q₄ are each independently of the others hydrogen orunsubstituted or substituted C₁-C₄alkyl,

G₁ und G₂ are halogen,

B is an organic bridge member,

A₂ and A₃ are each independently of the other as defined for A₁, or oneof A₂ and A₃ is hydrogen or unsubstituted or substituted C₁-C₄alkyl,phenyl or naphthyl and the other one of A₂ and A₃ is as defined for A₁,

(Z₂)₀₋₁ and (Z₃)₀₋₁ are each independently of the other 0 or 1 identicalor different fiber reactive radicals, and

b is the number 0 or 1.

The radicals Q₁, Q₂, Q₃ and Q₄ in the reactive dye of formula (1) asalkyl radicals are straight-chain or branched. The alkyl radicals may befurther substituted, for example by hydroxy, sulfo, sulfato, cyano or bycarboxy. The following radicals may be mentioned by way of example:methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl andtert-butyl, and also the corresponding hydroxy-, sulfo-, sulfate, cyano-or carboxy-substituted radicals. Preferred as substituents are hydroxy,sulfo and sulfate, especially hydroxy and sulfato, and preferablyhydroxy.

Q₁ and Q₄ are preferably hydrogen or C₁-C₄alkyl, especially hydrogen.

Q₂ and Q₃ are preferably each independently of the other hydrogen orunsubstituted or hydroxy-, sulfo-, sulfato-, cyano- orcarboxy-substituted C₁-C₄alkyl. According to an embodiment of interest,one of the radicals Q₂ and Q₃ is hydroxy-, sulfo-, sulfate, cyano- orcarboxy-substituted C₁-C₄alkyl, and the other of the radicals Q₂ and Q₃is hydrogen or C₁-C₄alkyl, especially hydrogen.

Q₂ and Q₃ are especially preferably each independently of the otherhydrogen or C₁-C₄alkyl, especially hydrogen.

G₁ und G₂ are preferably each independently of the other chlorine orfluorine, especially fluorine.

The following come into consideration as organic bridge members B, forexample:

C₂-C₁₂alkylene radicals, especially C₂-C₆alkylene radicals, which may beinterrupted by 1,2 or 3 members from the group —NH—, —N(CH₃)— and —O—,especially —O—, and are unsubstituted or substituted by hydroxy, sulfo,sulfato, cyano or by carboxy,

preferred substituents of the alkylene radicals mentioned for B beinghydroxy, sulfo and sulfato, especially hydroxy;

C₅-C₉cycloalkylene radicals, such as especially cyclohexylene radicals,that are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, sulfa, halogen or by carboxy, especially byC₁-C₄alkyl;

methylene-cyclohexylene-methylene radicals that are unsubstituted orsubstituted in the cyclohexylene ring by C₁-C₄alkyl;

C₁-C₆alkylenephenylene, or preferably phenylene, that is unsubstitutedor substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfatohalogen or by carboxy.

Also suitable as a radical of formula —N(Q₂)—B—N(Q₃)— is a radical ofthe formula

Preferably B is a C₂-C₁₂alkylene radical which may be interrupted by 1,2 or 3 members from the group —NH—, —N(CH₃)— and —O— and isunsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or bycarboxy; or

a phenylene radical that is unsubstituted or substituted by C₁-₄alkyl,C₁-C₄alkoxy, C₂-C₄-alkanoylamino, sulfo, halogen or by carboxy.

B is especially a C₂-C₁₂alkylene radical which may be interrupted by 1,2 or 3 members from the group —NH—, —N(CH₃)— and —O—, especially —O—,and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano orby carboxy. The alkylene radical is preferably unsubstituted orsubstituted by hydroxy, sulfo or by sulfato, especially by hydroxy.

B is more especially a C₂-C₂alkylene radical, especially a C₂-C₆alkyleneradical, which may be interrupted by 1, 2 or 3 —O— members and isunsubstituted or substituted by hydroxy.

Bridge members B of special interest are C₂-C₆alkylene radicals.

Fibre-reactive radicals are to be understood as meaning those which arecapable of reacting with the hydroxyl groups of cellulose, the amino,carboxyl, hydroxyl and thiol groups in wool and silk, or with the aminoand possibly carboxyl groups of synthetic polyamides, to form covalentchemical bonds. The fibre-reactive radicals are as a rule bonded to thedye radical directly or via a bridge member. Suitable fibre-reactiveradicals are, for example, those which contain at least one substituentwhich can be split off on an aliphatic, aromatic or heterocyclicradical, or in which the radicals mentioned contain a radical which iscapable of reaction with the fibre material, for example a vinylradical.

Preferably fiber reactive radicals Z₁, Z₂ and Z₃ independently of theother have the formula

in which

Hal is chlorine or bromine;

X₁ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T₁ independently has the meaning of X₁, or is a substituent which is notfiber reactive or a fiber reactive radical of the formula

in which

R₁, R_(1a) and R_(1b) independently of one another are each hydrogen orC₁-C₄alkyl,

R₂ is hydrogen, C₁-C₁alkyl which is unsubstituted or substituted byhydroxyl, sulfo, sulfato, carboxyl or cyano or a radical

R₃ is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen,C₁-C₄alkoxycarbonyl,

C₁-C₄alkanoyloxy, carbamoyl or the group —SO₂—Y,

alk and alk₁ independently of one another are linear or branchedC₁-C₆alkylene,

arylene is a phenylene or naphthylene radical which is unsubstituted orsubstituted by sulfo,

carboxyl, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,

Q is a radical —O— or —NR₁— in which R₁ is as defined above,

W is a group —SO₂—NR₂—, —CONR₂— or —NR₂CO—, in which R₂ is as definedabove,

Y is vinyl or a radical —CH₂CH₂—U and U is a group which can be splitoff under alkaline conditions,

Y₁ is a group —CH(Hal)CH₂-Hal or —C(Hal)=CH₂ and Hal is chlorine orbromine and

I and m independently of one another are an integer from 1 to 6 and n isthe number 0 or 1; and

X₂ is halogen or C₁-C₄alkylsulfonyl;

X₃ is halogen or C₁-C₄alkyl and

T₂ is hydrogen, cyano or halogen.

A group U which can be split off under alkaline conditions is, forexample, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₁-C₄alkyl)₂. U is preferably a group ofthe formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, inparticular —Cl or —OSO₃H, and particularly preferably —OSO₃H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- orβ-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl,β-chloroethyl or β-sulfatoethyl, and in particular vinyl orβ-sulfatoethyl.

R₁, R_(1a), and R_(1b) Independently of one another are each preferablyhydrogen, methyl or ethyl, and particularly preferably hydrogen.

R₂ is preferably hydrogen or C₁-C₄alkyl, such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl or tertbutyl, and particularlypreferably hydrogen, methyl or ethyl. R₂ is particularly preferablyhydrogen.

R₃ is preferably hydrogen.

I and m independently of one another are preferably the number 2, 3 or4, and particularly preferably the number 2 or 3.

Especially preferably, 1 is the number 3 and m is the number 2.

Substituents T₁ which are not fiber reactive are, for example, thefollowing radicals:

hydroxyl;

C₁-C₄alkoxy, for example methoxy, ethoxy, n- or isopropoxy or n-, sec-,iso- or tert-butoxy, in particular methoxy or ethoxy; the radicalsmentioned are unsubstituted or substituted in the alkyl moiety, forexample by C₁-C₄alkoxy, hydroxyl, sulfo or carboxyl;

C₁-C₄alkylthio, for example methylthio, ethylthio, n- or isopropylthioor n-butylthio; the radicals mentioned are unsubstituted or substitutedin the alkyl moiety, for example by C₁-C₄alkoxy, hydroxyl, sulfo orcarboxyl;

amino;

N-mono- or N,N-di-C₁-C₆alkylamino, preferably N-mono- orN,N-di-C₁-C₄alkylamino; the radicals mentioned are unsubstituted,uninterrupted or interrupted in the alkyl moiety by oxygen orsubstituted in the alkyl moiety, for example by C₂-C₄alkanoylamino,

C₁-C₄alkoxy, hydroxyl, sulfo, sulfato, carboxyl, cyano, carbamoyl orsulfamoyl; examples are N-methylamino, N-ethylamino, N-propylamino,N,N-di-methylamino or N,N-di-ethylamino, N-β-hydroxyethylamino,N,N-dihydroxyethylamino, N-2-(hydroxyethoxy)ethylamino,N-2-(β-hydroxyethoxy)ethylamino, N-2-[2-(β-hydroxyethoxy)]ethylamino,N-β-sulfatoethylamino, N-β-sulfoethylamino, N-carboxymethylamino,N-β-carboxyethylamino, N-α,β-dicarboxyethylamino,N-α,γ-dicarboxypropylamino, N-ethyl-N-β-hydroxyethylamino orN-methyl-N-β-hydroxyethylamino; C₅-C₇cycloalkylamino, for examplecyclohexylamino, which includes both the unsubstituted radicals and theradicals substituted in the cycloalkyl ring, for example by C₁-C₄alkyl,in particular methyl, or carboxyl;

phenylamino or N—C₁-C₄alkyl-N-phenylamino, which includes both theunsubstituted radicals and the radicals substituted in the phenyl ring,for example by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, carboxyl,carbamoyl, sulfo or halogen, for example 2-, 3- or 4-chlorophenylamino,2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphanylamino, 2-, 3- or4-sulfophenylamino, disulfophenylamino or 2-, 3- or4-carboxyphenylamino; naphthylamino which is unsubstituted orsubstituted in the naphthyl ring, for example by sulfo, preferably theradicals substituted by 1 to 3 sulfo groups, for example 1- or2-naphthylamino, 1-sulfo-2-naphthylamino, 1,5-disulfo-2-naphthylamino or4,8-disulfo-2-naphthylamino; or

benzylamino which is unsubstituted or substituted in the phenyl moiety,for example by C₁-C₄alkyl, C₁-C₄alkoxy, carboxyl, sulfo or halogen.

A radical T₁ which is not fiber reactive is preferably C₁-C₄alkoxy,C₁-C₄alkylthio, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino whichare optionally substituted in the alkyl moiety by hydroxyl, sulfato orsulfo, morpholino, phenylamino or N—C₁-C₄alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl ring by sulfo, carboxyl,acetylamino, chlorine, methyl or methoxy and in which the alkyl isunsubstituted or substituted by hydroxyl, sulfo or sulfato, ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups.

Particularly preferred radicals T₁ which are not fiber reactive areamino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-β-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, N-β-sulfatoethylamino, N-β-sulfoethylamino,morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylaminoor N—C₁-C₄-alkyl-N-phenylamino.

X, is preferably halogen, for example fluorine, chlorine or bromine, andparticularly preferably chlorine or fluorine.

Halogen T₂, X₂ and X₃ are, for example, fluorine, chlorine or bromine,in particular chlorine or fluorine.

C₁-C₄alkylsulfonyl X₂ is, for example, ethylsulfonyl or methylsulfonyl,and in particular methylsulfonyl.

C₁-C₄alkyl X₃ is, for example, methyl, ethyl, n- or iso-propyl or n-,iso or tert-butyl, and in particular methyl.

X₂ and X₃ independently of one another are preferably chlorine orfluorine.

T₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and alk₁ independently of one another are, for example, a methylene,ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6hexyleneradical or branched isomers thereof.

alk and alk₁ independently of one another are preferably each aC₁-C₄alkylene radical, and particularly preferably an ethylene radicalor propylene radical.

arylene is preferably a 1,3- or 1,4-phenylene radical which isunsubstituted or substituted, for example by sulfo, methyl, methoxy orcarboxyl, and particularly preferably an unsubstituted 1,3- or1,4-phenylene radical.

Q is preferably —NH— or —O—, and particularly preferably —O—.

W is preferably a group of the formula —CONH— or —NHCO—, in particular agroup of the formula —CONH—.

n is preferably the number 0.

The reactive radicals of the formulae (4a) to (4f) are preferably thosein which V is a group of the formula —CONH—. R₁, R₂ and R₃ are eachhydrogen, Q is the radical —O— or —NH—, alk and alk, independently ofone another are each ethylene or propylene, arylene is phenylene whichis unsubstituted or substituted by methyl, methoxy, carboxyl or sulfo, Yis vinyl or β-sulfatoethyl, Y₁ is —CHBr—CH₂Br or —CBr═CH₂ and n is thenumber 0.

A fibre-reactive radical Z₁, Z₂ and Z₃ is particularly preferably aradical of the formula (3a), (3c), (3d), (3e) or (3f), in which Y isvinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine, R₂ and R_(1a)are hydrogen, m is the number 2 or 3, X₁ is halogen, T₁ is C₁-C₄alkoxy,C₁-C₄alkylthio, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino whichare unsubstituted or substituted in the alkyl moiety by hydroxyl,sulfato or sulfo, morpholino, phenylamino or N—C₁-C₄alkyl-N-phenylaminowhich are unsubstituted or substituted in the phenyl ring by sulfo,carboxyl, acetylamino, chlorine, methyl or methoxy and in which thealkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups, or a fibre-reactive radical of the formula

in particular (4b′), (4c′) or (4d′), in which

Y is as defined above and

Y₁ is a group —CH(Br)—CH₂Br or —C(Br)═CH₂.

Preferred are dyes of the formula (1) which contain 1 or 2, inparticular 2, fiber reactive radicals Z₁.

Preferred are dyes of the formula (2) which do not contain fiberreactive radicals Z₂ and Z₃.

When one of A₂ and A₃ is unsubstituted or substituted C₁-C₄alkyl, phenylor naphthyl, it may be, for example, C₁-C₄alkyl that is unsubstituted orsubstituted by sulfo, sulfato, hydroxy, carboxy or by phenyl; or phenylor naphthyl each of which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, carboxy, sulfo or by halogen. Preference is given to phenylthat is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,carboxy, sulfo or by halogen.

Preferably A₂ and A₃ are each independently of the other the radical ofa monoazo, polyazo, metal-complexed azo, anthraquinone, phthalocyanine,formazan or dioxazine chromophore having at least one sulfo group.

A radical A₁, A₂ or A₃ as the radical of a monoazo, polyazo,metal-complexed azo, anthra-quinone, phthalocyanine, formazan ordioxazine chromophore may have the substituents customary in organicdyes bonded to its base structure.

The following may be mentioned as examples of substituents in theradicals A₁, A₂ and A₃: alkyl groups having from 1 to 4 carbon atoms,such as methyl, ethyl, propyl, isopropyl or butyl, it being possible forthe alkyl radicals to be further substituted e.g. by hydroxy, sulfo orby sulfato; alkoxy groups having from 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible forthe alkyl radicals to be further substituted e.g. by hydroxy, sulfo orby sulfato; phenyl that is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or by sulfo; acylamino groups having from1 to 8 carbon atoms, especially such alkanoylamino groups, e.g.acetylamino or propionylamino; benzoyl-amino that is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or bysulfo; phenylamino that is unsubstituted or substituted in the phenylring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or by sulfo;N,N-di-β-hydroxyethylamino; N,N-di-β-sulfato-ethylamino;sulfobenzylamino; N,N-disulfobenzylamino; alkoxycarbonyl having from 1to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl; alkylsulfonyl having from 1 to 4 carbon atoms, such asmethylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; amino; cyano;halogen, such as fluorine, chlorine or bromine; carbamoyl;N-alkyl-carbamoyl having from 1 to 4 carbon atoms in the alkyl radical,such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono- orN,N-di-alkylsulfamoyl each having from 1 to 4 carbon atoms, such asN-methylsulfonamoyl, N-thylsulfamoyl, N-propylsulfamoyl,N-isopropylsulfamoyl or N-butylsulfamoyl, it being possible for thealkyl radicals to be further substituted e.g. by hydroxy or by sulfo;N-(β-hydroxyethylisulfamoyl; N,N-di(β-hydroxyethyl)-sulfamoyl;N-phenylsulfamoyl that is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or by sulfo; ureido; hydroxy; carboxy;sulfomethyl or sulfo.

When A₁, A₂ and A₃ are the radical of a monoazo, polyazo ormetal-complexed azo chromophore, the following radicals, especially,come into consideration:

Chromophore radicals of a mono- or dis-azo dye of formulaD-N═N-(M-N═N)_(u)—K—  (5),-D-N═N-(M-N═N)_(u)—K   (6)or-D-N═N—K—N═N-D*-   (7),wherein D und D* independently of the other are the radicals of a diazocomponent of the benzene or naphthalene series, M is the radical of amiddle component of the benzene or naphthalene series, K is the radicalof a coupling component of the benzene, naphthalene, pyrazolone,6-hydroxypyridone-(2) or acetoacetic acid arylamide series and u is thenumber 0 or 1, it being possible in the case of azo dyes for D, D*, Mand K to carry customary substituents, e.g. C₁-C₄alkyl or C₁-C₄alkoxyeach of which is unsubstituted or may be further substituted by hydroxy,sulfo or by sulfato; halogen; carboxy; sulfo; nitro; cyano;trifluoromethyl; sulfamoyl; carbamoyl; amino; ureido; hydroxy; carboxy;sulfomethyl; C₂-C₄alkanoylamino; benzoylamino that is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or bysulfo; phenyl that is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or by sulfo. Also suitable are the metalcomplexes derived from the above dye radicals of formulae (5), (6) and(7), especially dye radicals of a 1:1 copper-complexed azo dye of thebenzene or naphthalene series wherein the copper atom is bonded to agroup capable of metallation, e.g. a hydroxy group, on each side in theortho-position to the azo bridge.

The radicals of formulae (5), (6) and (7) are preferably those offormula

wherein

(R₄)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, ureido, sulfamoyl,carbamoyl, sulfomethyl, halogen, nitro, cyano, trifluoromethyl, amino,hydroxy, carboxy and sulfo,

(R₅)₀₋₂ denotes from 0 to 2 identical or different substituents from thegroup hydroxy, amino, N-mono-C₁-C₄alkylamino, N,N-di-C₁-C₄alkylamino,C₂-C₄alkanoylamino and benzoylamino;

wherein

(R₅)₀₋₂ is as defined above;

wherein

(R₆)₀₋₃ und (R₇)₀₋₃ independently of the other denotes from 0 to 3identical or different substituents from the group C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo;

wherein

R₈ und R₁₀ are each independently of the other hydrogen, C₁-C₄alkyl orphenyl, and

R₉ hydrogen, cyano, carbamoyl or sulfomethyl;

wherein

(R₁₂)₀₋₃ denotes from 0 to 3 identical or different substituents fromthe group C₁-C₄alkyl,

C₁-C₄alkoxy, halogen, amino, carboxy and sulfo, and

(R₁₁)₀₋₃ and (R₁₃)₀₋₃ independently of the other are as defined for(R₄)₀₋₃;

wherein

(R₁₁)₀₋₃ and (R₁₃)0-3 independently of the other are as defined above

(R₁₄)₀₋₂ denotes from 0 to 2 identical or different substituents fromthe group C₁-C₄alkyl.

C₁-C₄alkoxy, halogen, carboxy, sulfo, hydroxy, amino,N-mono-C₁-C₄alkylamino, N,N-di-C₁-C₄alkylamino, C₂-C₄alkanoylamino andbenzoylamino.

When A₁, A₂ and A₃ are the radical of a formazan dye the followingradicals, especially, come into consideration:

wherein

the benzene nuclei do not contain any further substituents or arefurther substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylsulfonyl,halogen or by carboxy.

When A₁, A₂ and A₃ are the radical of a phthalocyanine dye the followingradicals, especially, come into consideration:

wherein

Pc is the radical of a metal phthalocyanine, especially the radical of acopper or nickel phthalocyanine,

W′ is —OH and/or —NR₁₈R₁₆′ and R₁₆ and R₁₆′ are each independently ofthe other hydrogen or

C₁-C₄alkyl that is unsubstituted or substituted by hydroxy or by sulfo,

R₁₅ is hydrogen or C₁-C₄alkyl,

A is a phenylene radical that is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy,

halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical and

k is from 1 to 3.

When A₁, A₂ and A₃ are the radical of a dioxazine dye the followingradicals, especially, come into consideration:

wherein

A′ is a phenylene radical that is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy,

halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical,

r independently is the number 0, 1 or 2, preferably 0 or 1, and

v and v′ are each independently of the other the number 0 or 1.

When A₁, A₂ and A₃ are the radical of a anthrachinon dye the followingradicals, especially, come into consideration:

wherein

G is a phenylene radical that is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy,

halogen, carboxy or by sulfo or is a cyclohexylene, phenylenemethyleneor C₂-C₆alkylene radical.

Preferably b in the dye of formula (2) is the number 1.

Special interest is accorded to reactive dyes of formulae

In a particular preferred embodiment of the present invention the dyesof formulae (1.1), (1.4), (1.9), (1.12), (1.14), (1.15), (1.19); (1.23),(1.25), (1.27), (1.29), (1.33), (1.35), (1.39), (1.40). (1.44), (1.45),(1,46) to (1.49), (2.4), (2.14), (2.15) and (2.17) are used.

The reactive dyes of formulae (1) and (2) are known or can be obtainedanalogously to known compounds, e.g. by customary diazotisation,coupling and condensation reactions.

Preferred as a di, tri or tetramer of a C₂-C₄-oxyalkylene or a mono- ordi-C₁-C₄-alkyl ether of a C₂-C₄-Oxyalkylene is a C₂-C₃-alkylene glycol,for example, diethylene glycol, triethylene glycol, dipropylene glycol,tripropylene glycol, especially dipropylene glycol or tripropyleneglycol, more especially dipropylene glycol, in an amount of, forexample, from 10 to 60% by weight, preferably from 20 to 50% by weight,especially from 25 to 45% by weight and more especially from 35 to 45%by weight based on the total weight of the ink.

In addition to the components mentioned above, the ink in accordancewith the inventive process can contain, as required, various additivessuch as a surfactants, viscosity adjusting agents, buffers, antifoamagents or substances that inhibit the growth of fungi and/or bacteria,etc.

The inks may comprise thickeners of natural or synthetic origin interalia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commerciallyavailable alginate thickeners, starch ethers or locust bean flourethers, especially sodium alginate on its own or in admixture withmodified cellulose, e.g. methylcellulose, ethylcellulose,carboxymethyl-cellulose, hydroxyethylcellulose,methylhydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropylmethylcellulose, especially with preferably from 20 to 25% by weightcarboxy-methylcellulose. Synthetic thickeners that may be mentioned are,for example, those based on poly(meth)acrylic acids,poly(meth)acrylamides or polyvinyl pyrrolidones.

The inks comprise such thickeners, for example, in an amount of from0.01 to 2% by weight, especially from 0.01 to 1.2% by weight and moreespecially from 0.02 to 1% by weight, based on the total weight of theink.

With or without such viscosity adjusting agent the viscosity of the inkis adjusted to be from 6 to 14 mPa·s at 25° C., especially from 7 to 12mPa s at 25° C. and more especially from 8to 11 mPa s at 25° C.

In a particularly preferred embodiment of the present invention polyC₂-C₄-alkyleneglycol or the mono- or di-C₁-C₄-alkyl ether of polyC₂-C₄-alkyleneglycol is used as a viscosity adjusting agent, thealkylene moieties of which nay be straight chained or branched,especially poly C₂-C₃-alkyleneglycol, such as, polyethylene glycol,polypropylene glycol or a mixed ethylene oxide/propylene oxidecopolymerisate, and more especially a mixed ethylene oxide/propyleneoxide copolymerisate. The molar mass is, for example, from 1,000 to35,000 g/mol, preferably from 2,000 to 25,000 g/mol and especially from3,000 to 20,000. The said compounds are commercially available, forexample, as P41-type polyglycols (Clariant).

The organic solvent (II) is used solely, although alternatively, amixture of two or more organic solvents may be used. Further organicsolvents which may be used in combination with component (II) arewater-miscible organic solvents, for example C₁-C₄-alcohols, such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol and iso-butanol; amides, e.g. dimethylformamide anddimethylacetamide; ketones or ketone alcohols, e.g. acetone anddiacetone alcohol; ethers, e.g. tetrahydrofuran and dioxane;nitrogen-containing heterocyclic compounds, e.g. N-methyl-2-pyrrolidoneand 1,3-dimethyl-2-imidazolidone; glycols or thioglycols, e.g. ethyleneglycol, propylene glycol, butylene glycol, thiodiglycol and hexyleneglycol; further polyols, e.g. glycerol and 1,2,6-hexanetriol; andC₁-C₄alkyl ethers of polyhydric alcohols, e.g. 2-methoxyethanol,2-(2-ethoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-[2-(2-methoxyethoxyethoxy]-ethanol and2-[2-(2-ethoxyethoxy)-ethoxylethanol; preferably N-methyl-2-pyrrolidone,glycerol or especially 1,2-propylene glycol.

Preferably, the organic solvent (II) is used solely without any furtherorganic solvent.

The inks may also comprise solubilisers, e.g. ε-caprolactam.

The inks may also comprise buffer substances. e.g. borax, borates,phosphates, poly-phosphates or citrates. Examples that may be mentionedinclude borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodiumpentapolyphosphate and sodium citrate. They are used especially inamounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% byweight, based on the total weight of the ink, in order to establish a pHvalue, for example, from 4 to 10, especially from 5 to 9.5 and moreespecially from 8 to 9.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionicsurfactants. As humectants in the inks according to the invention therecome into consideration, for example, urea or a mixture of sodiumlactate (advantageously in the form of a 50% to 60% aqueous solution)and glycerol and/or propylene glycol in amounts of preferably from 0.1to 30% by weight, especially from 2 to 30% by weight The inks inaddition may contain the sodium salt of nitrobenzene sulfonic acid.

The inks may also comprise customary additives, such as antifoam agentsor especially substances that inhibit the growth of fungi and/orbacteria. Such additives are usually used in amounts of from 0.01 to 1%by weight, based on the total weight of the ink.

As preservatives there come into consideration formaldehyde-releasingagents. e.g. paraformaldehyde and trioxane, especially aqueous, forexample 30 to 40% by weight formaldehyde solutions, imidazole compounds,e.g. 2-(4-thiazolyl)benzimidazole, thiazole compounds, e.g.1,2-benzisothiazolinone or 2-n-octyl-isothiazolin-3-one, iodinecompounds, nitriles, phenols, haloalkylthio compounds and pyridinederivatives, especially 1,2-benzisothiazolin-3one or2-n-octyl-isothiazolin-3-one. As an example for a broad spectrum biocidefor the preservation against spoilage from bacteria, yeasts and fungi a20% by weight solution of 1,2benzisothiazolin-3one in dipropylene glycol(Proxel™ GXL) can be used.

The inks may comprise further ingredients such as fluorinated polymersor telomers for example polyethoxy perfluoro alcohols (Forafac®products) in an amount of from 0.01 to 1% by weight based on the totalweight of the ink.

It is preferred that the surface tension is adjusted to range from 20 to40 dyne/cm at 25° C., especially from 20 to 35 dyne/cm at 25° C. andmore especially from 25 to 30 dyne/cm at 25° C.

Furthermore it is preferred that the conductivity of the ink is adjustedto range from 1 to 6 mS/cm at 25° C. and especially from 2 to 5 mS/cm at25° C.

The inks can be prepared in customary manner by mixing the individualconstituents together in the desired amount of water.

It has been found that the inks described above can be advantageouslyapplied to the textile fiber materials by means of an ink-jet printingdevice provided with at least one ink-jet print head which comprises

-   -   a nozzle layer (a) defining a plurality of ejection nozzles,    -   an ink supply layer (b) which is formed from a porous material        having a multitude of small interconnected pores so as to allow        passage of ink therethrough, the ink supply layer featuring a        plurality of connecting bores (holes) from the rear surface to        the front surface, each connecting bore being aligned so as to        connect between a corresponding one of the ejection nozzles and    -   a deflection layer (c), comprising a plurality of transducers        related to the connecting bores for ejecting ink droplets out        through the nozzles.

The ink-jet print head applied in accordance with the present inventionmay additionally comprise

-   -   an ink cavity layer (d), associated with the rear surface of the        ink supply layer (b) having a plurality of apertures, each        aperture being positioned to correspond to one of the connecting        bores of the ink supply layer so as to at least partially define        a corresponding ink cavity.

The ink-jet print head applied in accordance with the present inventioncomprises a layered structure a key element of which is the ink supplylayer (b) made of a porous material. The ink supply layer (b) is indirect communication with both the ink reservoir and the individual inkcavities of the connecting bores (holes) and/or the individual inkcavities of the ink cavity layer (d), thereby acting as hydrauliclinkage between the ink main supply and the individual ink cavities.

The porous material includes, for example, sintered material, mostpreferably, sintered stainless steel.

The ink cavity layer (d) may be omitted. In this case, the deflectionlayer directly adjoins the ink supply layer.

The ink-jet print head used in accordance with the present invention isdescribed in detail in U.S. Pat. No. 5,940,099, the disclosure of whichis incorporated herein.

The ink-jet print head applied in accordance with the present inventionbelongs to the category of drop on demand systems, wherein the ink dropsare ejected selectively as required.

The transducers are, for example, piezoelectric crystals (piezoelectrictype) or thermoelectric elements (thermal bubble jet type), preferablypiezoelectric crystals.

The ejection of ink drops using a device according to one embodiment ofthe present invention is accomplished as follows:

A pressure pulse is imparted to a volume of ink in an ink cavity throughthe deflection of a thin deflection plate, or diaphragm, located on topof the ink cavity. The plate is deflected downward by the action of apiezoceramic crystal whenever a voltage is applied across itselectrodes, one of which is in electrical contact with the usuallymetallic deflection plate. The pressure pulse created by the downwardbending of the deflection plate drives the ink towards and through anoutlet, having a convergent nozzle at its outlet end, causing theejection of a drop of a specific size. When the piezoelectric crystal isde-energized, it returns to its equilibrium position, reducing thepressure in the ink cavity and causing the meniscus at the outlet end toretract. The retracted meniscus generates a capillary force which actsto pull ink from an ink reservoir through the porous material of the inksupply layer (b) into the ink cavity and into the connecting bores(holes) related to the nozzle. The refilling process ends when themeniscus regains its equilibrium position.

The micron grade and the surface area of the porous material which isopen for flow into the ink cavity has a crucial impact on the refilltime of the ink cavities and hence on the maximum drop ejection rate, orfrequency. The ink according to the inventive process moves through theinterconnected pores and channels of the ink supply layer (b) withsuitable flow resistances in order to realize system performance whichallows for high ejection frequencies, for example, 5 to 100 kHz,preferably 10 to 50 kHz and especially 20 to 40 kHz Moreover the inkscause no dogging of the ejection nozzles. Feathering or blurring andblotting on the both is omitted. The inks are storage stable, i.e. nodeposition of solid matter is observed in the course of storage.

Further embodiments of suitable inkjet print head configurationscomprising an ink supply layer which is formed from a porous materialare described in U.S. Pat. No. 5,940,099, all of which can be used inthe process according to the present invention.

In a preferred embodiment of the present invention the ink-jet printhead comprises

-   -   a nozzle layer (a) defining a plurality of ejection nozzles,    -   an ink supply layer (b) having a front surface associated with        the nozzle layer and a rear surface associated with a cavity        layer (d), the ink supply layer being formed with a plurality of        connecting bores (holes) from the rear surface to the front        surface, each connecting bore being aligned so as to connect        between a corresponding one of the ink cavities and a        corresponding one of the ejection nozzles, wherein the ink        supply layer additionally features (i) a pattern of ink        distribution channels formed in the front surface, and (ii) at        least one ink inlet bore passing from the rear surface to the        front surface and configured so as to be in direct fluid        communication with at least part of the pattern of ink        distribution channels, the pattern of ink distribution channels        and the at least one ink inlet bore together defining part of an        ink flow path which passes from the rear surface through the at        least one ink inlet bore to the pattern of ink distribution        channels on the front surface, and through the porous material        to the plurality of ink cavities.    -   a deflection layer (c), comprising a plurality of transducers        related to the connecting bores for ejecting ink droplets out        through the nozzles.

The location of ink distribution channels on the front surface ensuresthat ink flow through the porous material of ink supply layer occursthrough the bulk of the layer. Preferably ink distribution channels aredistributed over the front surface in such a pattern that eachconnecting bore is approximately the same distance from its nearest inkdistribution channel. In the typical case that the connecting boresdefine an array on the front surface having two row directions, thepattern of ink distribution channels preferably includes a plurality ofchannels deployed substantially parallel to one of the row directionsand interposed between adjacent rows of the connecting bores. The inkflow path is particularly effective for providing a sufficient andgenerally uniform ink supply to the porous layer across an entire arrayof ink cavities.

The ink-jet print head used in accordance with the present invention isa multi-nozzle print head, the individual nozzles of which areadvantageously arranged as an array made up of horizontal rows which arehorizontally staggered, or skewed, with respect to one another,comprising, for example, 512 nozzles staggered in a 32×16 array.

The ink-jet print head used in accordance with the preferred embodimentof the present invention is described in detail in U.S. Pat. No.6,439,702, the disclosure of which is incorporated herein.

Further embodiments of suitable ink-jet print head configurationscomprising an ink supply layer which is formed from a porous materialare described in U.S. Pat. No. 6,439,702, all of which can be used inthe process according to the present invention.

The ink-jet printing device used in accordance with the presentinvention comprises at least one of the inkjet print heads describedabove. Preferably, the printing device uses at least 3 process colors,for example 3, 4, 5 or 6 process colors, preferably 6 process colors,wherein each color is processed with at least one print head, forexample 1, 2, 3, 4, 5, 6 or 7 printing heads, preferably 7 printingheads.

The present invention allows textile fiber materials to be printed witha speed of at least 50 m²/h, preferably in the range of 100 to 250 m²/h,especially 150 to 250 m²/h.

Textile fibre materials that come into consideration are especiallyhydroxy-group-containing fibre materials. Preference is given tocellulosic fibre materials that consist wholly or partly of cellulose.Examples are natural fibre materials, such as cotton, linen and hemp,and regenerated fibre materials, for example viscose and lyocell.Special preference is given to viscose and cotton, especially cotton.The said fibre materials are preferably in the form of textile wovenfabrics, knitted fabrics or webs.

According to a preferred embodiment of the present invention, prior toprinting the fibre material is subjected to a pretreatment in which thefibre material to be printed is first treated with an aqueous alkalineliquor and the treated fibre material is optionally dried. The aqueousalkaline liquor comprises at least one of the customary bases used forfixing the reactive dyes in conventional reactive printing processes.The base is used, for example, in an amount of from 10 to 100 g/l ofliquor, preferably from 10 to 50 g/l of liquor. Suitable bases are, forexample, sodium carbonate, sodium hydroxide, disodium phosphate,trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogencarbonate, aqueous ammonia or sources of alkali, such as sodiumchloroacetate or sodium formate. It is preferable to use sodium hydrogencarbonate, sodium carbonate or a mixture of water glass and sodiumcarbonate. The pH value of the alkaline liquor is generally from 7.5 to13.5, preferably from 8.5 to 12.5. In addition to the bases, the aqueousalkaline liquor may also comprise further additives, e.g. hydrotropicagents. The hydrotropic agent preferably used is urea, which is used,for example, in an amount of from 25 to 200 g/l of liquor, preferablyfrom 50 to 150 g/l of liquor. In addition the liquor for pretreating thefibre material may contain the sodium salt of nitrobenzene sulfonic acidin an amount of 1 to 100 g/l of liquor and a copolymer of acrylamidebasis in an amount of 50 to 500 g/l of liquor as well as a silicon basedsoftener, for example a Megasoft® product in an amount of 0,1 to 100 g/lof liquor.

An excellent colour performance is obtained with the followingpre-treatment of the fibre material, which is a further object of theinvention, whereby the fabric is pre-treated, for example by printing orpadding or jet dyeing , preferably pad-dyed with the liquor comprising apad dyeing auxiliary comprising acrylic acid amide/acrylic acidcopolymer from acrylic acid amide and acrylic acid monomer in an amountof 0.5 to 5 g/l of liquor, urea in an amount of 50 to 150 g/l of liquor,a base, preferably soda ash, in an amount of 20 to 80 g/l of liquor,sodium salt of nitrobenzene sulfonic acid in an amount of 5 to 50 g/l ofliquor, a softener based on a amino functional siloxane in an amount of10 to 100 g/l of liquor and optionally a salt, preferably sodiumchloride, in an amount of 50 to 200 g/l of liquor.

Preferably the fibre material is dried after the above pretreatment

After printing, the fibre material is advantageously dried, preferablyat temperatures of up to 150° C., especially from 80 to 120° C., andthen, where necessary, subjected to a heat treatment process in order tocomplete the print, that is to say to fix the dye.

The heat treatment can be carried out, for example, by means of a hotbatch process, a thermosol process or, preferably, by means of asteaming process.

In the case of the steaming process the printed fibre material issubjected, for example, to treatment in a steamer with steam which isoptionally superheated, advantageously at a temperature of from 95 to180° C., more especially in saturated steam.

Subsequently the printed fibre material is generally washed off withwater in customary manner in order to remove unfixed dye.

Using the printing processes indicated above it is possible to printfibrous materials either in a single shade or in a variety of shades.When the printing is in one shade, the fibrous material can be printedover the entire surface or with a pattern. The use of a single ink is,of course, sufficient for that purpose, but the desired shade can alsobe created by printing with a plurality of inks of different shades.When the fibrous material is to receive a print having a plurality ofdifferent shades, the fibrous material can either be printed with aplurality of inks that each have the desired shade or printed in such amanner that the shade in question is created (for example by printingthe fibrous material with inks of different shades one on top ofanother, thus producing the required shade).

The prints produced are distinguished especially by a high tinctorialstrength and a high color brilliance as well as by good light-fastnessand wet-fastness properties.

The present invention relates also to an aqueous inks comprising

(I) at least one fiber reactive dye of formula (1) or (2), and

(II) a di, tri or tetramer of a C₂-C₄-oxyalkylene or a mono- ordi-C₁-C₄-alkyl ether of a di, tri or tetramer of a C₂-C₄-oxyalkylene,

said ink having a viscosity from 5 to 20 mPa s at 25° C., wherein thevariables associated with components (I) and (II) have the meanings andpreferences given above.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to percent by weight.Parts by weight relate to parts by volume in a ratio of kilograms tolitres.

EXAMPLE 1

a) Mercerised cotton satin fabric web is pad-dyed with a liquorcomprising 30 g/l of sodium carbonate (liquor pick-up 70%) and dried.

b) The cotton satin pretreated in accordance with step a) is printedwith an industrial piezoelectric drop on demand ink-jet printing device(Reggiani DReAM) at a speed of 150 m²/h. The device processes 6 colors(6 inks), wherein each process color is printed with 7 print heads(Aprion).

The inks are as follows:

a yellow aqueous ink containing:

-   -   6.5% by weight of the reactive dye of formula (1.45),    -   40.0% by weight of dipropylenglycol,    -   0.5% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   52.7% by weight of water;

an orange aqueous ink containing:

-   -   7.0% by weight of the reactive dye of formula (1.29),    -   40.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   52.3% by weight of water,

a red aqueous ink containing:

-   -   10.0% by weight of the reactive dye of formula (1.35),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   49.7% by weight of water,

a blue aqueous ink containing:

-   -   9.0% by weight of the reactive dye of formula (1.9),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   50.7% by weight of water;

a turquoise aqueous ink containing:

-   -   7.5% by weight of the reactive dye of formula (1.40),    -   40.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   51.8% by weight of water,

a black aqueous ink containing:

-   -   0.2% by weight of the reactive dye of formula (1.14),    -   10.6% by weight of the reactive dye of formula (1.23),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   48.9% by weight of water.

The print is dried on line with an integrated hot air dryer at 100° C. Ahigh quality multicolour print showing no blotting and having very goodfastness to washing is obtained.

EXAMPLE 2

For an excellent performance the above given example 1 is repeated usingthe following steps:

a) Mercerised cotton satin fabric web is pad-dyed with a liquorcomprising 2 g/l of a pad dyeing auxiliary comprising acrylic acidamide/acrylic add copolymer from acrylic add amide and acrylic acidmonomer, 100 g/l of urea, 40 g/l soda ash, 100 g/l of sodium chloride,20 g/l of sodium salt of nitrobenzene sulfonic add and 30 g/l of asoftener based on a amino functional siloxane (liquor pick-up 70%) anddried.

b) The cotton satin pretreated in accordance with step a) is printedwith an industrial piezoelectric drop on demand ink-jet printing device(Reggiani DReAM) at a speed of 150 m²/h. The device processes 6 colors(6 inks), wherein each process color is printed with 7 print heads(Aprion).

The inks are as follows:

a yellow aqueous ink containing:

-   -   6.5% by weight of the reactive dye of formula (1.45),    -   40.0% by weight of dipropylenglycol,    -   0.5% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perluoro alcohol (e.g. Forafa®        1110 D)    -   52.6% by weight of water,

an orange aqueous ink containing:

-   -   7.0% by weight of the reactive dye of formula (1.29),    -   40.0% by weight of dipropylenglyool,    -   0.04% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   52,3% by weight of water;

a red aqueous ink containing:

-   -   10.0% by weight of the reactive dye of formula (1.35),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac®        1110D)    -   49.6% by weight of water;

a blue aqueous ink containing:

-   -   9.0% by weight of the reactive dye of formula (1.9),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   50.7% by weight of water;

a turquoise aqueous ink containing:

-   -   7.5% by weight of the reactive dye of formula (1.40),    -   40.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac®        1110D)    -   51.7% by weight of water,

a black aqueous ink containing:

-   -   0.2% by weight of the reactive dye of formula (1.14),    -   10.6% by weight of the reactive dye of formula (1.23),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy pernuoro alcohol (e.g. Forafac®        1110D)    -   48.8% by weight of water.

The print is dried on line with an integrated hot air dryer at 100° C. Ahigh quality multicolour print showing no blotting and having very goodfastness to washing is obtained.

EXAMPLE 3

a) Causticities woven viscose fabric web is pad-dyed with a liquorcomprising 30 g/l of sodium carbonate and 100 g/l of urea (liquorpick-up 70%) and dried.

b) The causticized woven viscose fabric pretreated in accordance withstep a) is printed with an industrial piezoelectric drop on demandink-jet printing device (Reggiani DReAM) at a speed of 150 m²/h inanalogy to the process of example 1 using the inks of example 1. Theprint is dried on line with an integrated hot air dryer at 100° C. Ahigh quality multicolour print showing no blotting and having very goodfastness to washing is obtained.

EXAMPLE 4

a) Mercerised cotton satin fabric web is pad-dyed with a liquorcomprising 30 g/l of sodium carbonate (liquor pick-up 70%) and dried.

b) The cotton satin pretreated in accordance with step a) is printedwith an industrial piezoelectric drop on demand ink-jet printing device(Reggiani DReAM) at a speed of 150 m²/h. The device processes 6 colors(6 inks), wherein each process color is printed with 7 print heads(Aprion).

The inks are as follows:

a yellow aqueous ink containing:

-   -   6.8% by weight of the reactive dye of formula (1.44),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafa®        1110D)    -   52.5% by weight of water;

an orange aqueous ink containing:

-   -   7.2% by weight of the reactive dye of formula (1.27),    -   41.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.3% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched)    -   0.1% by weight of a polyethoxy perluom alcohol (e.g. Forafac®        1110D)    -   51.1% by weight of water;

a red aqueous ink containing:

-   -   8.0% by weight of the reactive dye of formula (1.33),    -   40.0% by weight of dipropylenglycol,    -   0.2% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched)    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac®        1110D)    -   51.4% by weight of water;

a blue aqueous ink containing:

-   -   9.0% by weight of the reactive dye of formula (1.4),    -   38.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy pernluoro alcohol (e.g. Forafac®        1110D)    -   52.6% by weight of water;

a turquoise aqueous ink containing:

-   -   7.5% by weight of the reactive dye of formula (1.39),    -   40.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfiluoro alcohol (e.g. Forafac®        1110D)    -   51.7% by weight of water,

a black aqueous ink containing:

-   -   0.3% by weight of the reactive dye of fornula (1.25),    -   10.0% by weight of the reactive dye of formula (1.1),    -   38.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac        1110D)    -   51.3% by weight of water.

The print is dried on line with an integrated hot air dryer at 100° C. Ahigh quality multicolour print showing no blotting and having very goodfastness to washing is obtained.

EXAMPLE 5

a) Causticized woven viscose fabric web is pad-dyed with a liquorcomprising 30 g/l of sodium carbonate and 100 g/l of urea (liquor pickup70%) and dried.

b) The cotton satin pretreated in accordance with step a) is printedwith an industrial piezoelectric drop on demand ink-jet printing device(Reggiani DReAM) at a speed of 150 m²/h. The device processes 6 colors(6 inks), wherein each process color is printed with 7 print heads(Aprion).

The inks are as follows:

a yellow aqueous ink containing:

-   -   10% by weight of the reactive dye of formula (2.17),    -   41.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac®        1110D)    -   46.6% by weight of water;

an orange aqueous ink containing:

-   -   8.0% by weight of a mixture of the reactive dyes of formula        (2.4), (2.14) und (2.15)    -   39.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy periluoro alcohol (e.g. Forafac®        1110D)    -   52.2% by weight of water;

a red aqueous ink containing:

-   -   8.0% by weight of the reactive dye of formula (2.22),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluoro alcohol (e.g. Forafac®        1110D),    -   51.3% by weight of water;

a blue aqueous ink containing:

-   -   9.0% by weight of the reactive dye of formula (1.12),    -   42.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perfluom alcohol (e.g. Forafac®        1110D)    -   48.6% by weight of water;

a turquoise aqueous ink containing:

-   -   7.5% by weight of the reactive dye of formula (1.40),    -   40.0% by weight of dipropylenglycol,    -   0.4% by weight of polyglycol (ethylene oxide/propylene oxide        copolymerisate, branched),    -   0.1% by weight of a polyethoxy perfluoro aloohol (e.g. Forafac®        1110D)    -   0.3% by weight of Proxel™ GXL,    -   51.7% by weight of water,

a black aqueous ink containing:

-   -   1.5% by weight of a mixture of the reactive dyes of formula        (1.46), (1.47), (1.48) und (1.49),    -   1.5% by weight of the reactive dye of formula (1.50),    -   7.0% by weight of the reactive dye of formula (1.1),    -   40.0% by weight of dipropylenglycol,    -   0.3% by weight of Proxel™ GXL,    -   0.1% by weight of a polyethoxy perruoro alcohol (e.g. Forafac®        1110D)    -   49.6% by weight of water.

The print is dried on line with an integrated hot air dryer at 100° C. Ahigh quality multicolour print showing no blotting and having very goodfastness to washing is obtained.

1. An ink-jet printing process for printing textile fibre materials,wherein the fiber materials are printed with an aqueous ink comprising(I) at least one fiber reactive dye, and (II) a di, tri or tetramer of aC₂-C₄-oxyalkylene or a mono- or di-C₁-C₄-alkyl ether of a di, tri ortetramer of a C₂-C₄-oxyalkylene, said ink having a viscosity from 5 to20 mPa s at 25° C., and wherein said ink is applied to the fibermaterial with an ink-jet print head comprising an ink supply layer (b)receiving ink from an external ink reservoir, said ink supply layerhaving a first side and a second side and comprising, a porous mediumhaving a plurality of pores therein and a plurality of holes extendingtherethrough, so as to allow passage of the ink.
 2. A process accordingto claim 1, wherein the fiber reactive dye is a dye of the formulaA₁-(Z₁)₁₋₃   (1 ) wherein A₁ is the radical of a monoazo, disazo,polyazo, metal-complexed azo, anthraquinone, phthalo-cyanine, formazanor dioxazine chromophore having at least one sulfo group, and (Z₁)₁₋₃ is1 to 3 identical or different fiber reactive radicals, or a dye of theformula

wherein Q₁, Q₂, Q₃ and Q₄ are each independently of the others hydrogenor unsubstituted or substituted C₁-C₄alkyl, G₁ und G₂ are halogen, B isan organic bridge member, A₂ and A₃ are each independently of the otheras defined for A₁, or one of A₂ and A₃ is hydrogen or unsubstituted orsubstituted C₁-C₄alkyl, phenyl or naphthyl and the other one of A₂ andA₃ is as defined for A₁, (Z₂)₀₋₁ and (Z₃)₀₋₁ are each independently ofthe other 0 or 1 identical or different fiber reactive radicals, and bis the number 0 or
 1. 3. A process according to claim 2, wherein Z₁, Z₂and Z₃ are each independently of the other a radical of the formula

in which Hal is chlorine or bromine; X₁ is halogen,3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl; T₁ independently hasthe meaning of X₁, or is a substituent which is not fiber reactive or afiber reactive radical of the formula

in which R₁, R_(1a) and R_(1b) independently of one another are eachhydrogen or C₁-C₄alkyl, R₂ is hydrogen, C₁-C₄alkyl which isunsubstituted or substituted by hydroxyl, sulfo, sulfato, carboxyl orcyano or a radical

R₃ is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen,C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy, carbamoyl or the group —SO₂—Y,alk and alk, independently of one another are linear or branchedC₁-C₆alkylene, arylene is a phenylene or naphthylene radical which isunsubstituted or substituted by sulfo, carboxyl, C₁-C₄alkyl, C₁-C₄alkoxyor halogen, Q is a radical —O— or —NR₁—, in which R₂ is as definedabove, W is a group —SO₂—NR₂—, —CONR₂— or —NR₂CO—, in which R₂ is asdefined above, Y is vinyl or a radical —CH₂—CH₂—U and U is a group whichcan be split off under alkaline conditions, Y₁ is a group—CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ and Hal is chlorine or bromine and I andm independently of one another are an integer from 1 to 6 and n is thenumber 0 or 1; and X₂ is halogen or C₁-C₄alkylsulfonyl; X₃ is halogen orC₁-C₄alkyl and T₂ is hydrogen, cyano or halogen.
 4. A process accordingto claim 2, wherein Z₁, Z₂ and Z₃ are each independently of the other aradical of the formula (3a), (3c), (3d), (3e) or (3f) according to claim3, in which Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine,R₂ and R_(1a) are hydrogen, m is the number 2 or 3, X₁ is halogen, T₁ isC₁-C₄alkoxy, C₁-C₄alkylthio, hydroxyl, amino, N-mono- orN,N-di-C₁-C₄alkylamino which are unsubstituted or substituted in thealkyl moiety by hydroxyl, sulfato or sulfo, morpholino, phenylamino orN—C₁-C₄alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxyand in which the alkyl is unsubstituted or substituted by hydroxyl,sulfo or sulfato, or naphthylamino which is unsubstituted or substitutedby 1 to 3 sulfo groups, or a fibre-reactive radical of the formula

in which Y is as defined above and Y₁ is a group —CH(Br)—CH₂—Br or—C(Br)═CH₂.
 5. A process according to claim 2, wherein the dye offormula (1) contains 1 or 2 fiber reactive radicals Z₁.
 6. A processaccording to claim 2, wherein B is a C₂-C₆alkylene radical, which may beinterrupted by 1, 2 or 3 —O— members and is unsubstituted or substitutedby hydroxy.
 7. A process according to claim 2, wherein G₁ und G₂ areeach independently of the other chlorine or fluorine.
 8. A processaccording claim 2, wherein A₁, A₂ and A₃ are each independently of theother a radical of the formula

wherein (R₄)₀₋₃ denotes from 0 to 3 identical or different substituentsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl, halogen,nitro, cyano, trifluoromethyl, amino, hydroxy, carboxy and sulfo,(R₅)₀₋₂ denotes from 0 to 2 identical or different substituents from thegroup hydroxy, amino, N-mono-C₁-C₄alkylamino, N,N-di-C₁-C₄alkylamino,C₂-C₄alkanoylamino and benzoylamino;

wherein (R₅)₀₋₂ is as defined above;

wherein (R₆)₀₋₃ und (R₇)₀₋₃ independently of the other denotes from 0 to3 identical or different selected from the group consisting ofC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo;

wherein R₈ und R₁₀ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl, and R₉ hydrogen, cyano, carbamoyl or sulfomethyl;

wherein (R₁₂)₀₋₃ denotes from 0 to 3 identical or different substituentsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen,amino, carboxy and sulfo, and (R₁₁)₀₋₃ and (R₁₃)₀₋₃ independently of theother are as defined for (R₄)₀₋₃;

wherein (R₁₁)₀₋₃ and (R₁₃)₀₋₃ independently of the other are as definedabove (R₁₄)₀₋₂ denotes from 0 to 2 identical or different substituentsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen,carboxy, sulfo, hydroxy, amino, N-mono-C₁-C₄alkylamino,N,N-di-C₁-C₄alkylamino, C₂-C₄alkanoylamino and benzoylamino;

wherein the benzene nuclei do not contain any further substituents orare further substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylsulfonyl,halogen or by carboxy;

wherein Pc is the radical of a metal phthalocyanine, W′ is —OH and/or—NR₁₆R₁₆′ and R₁₆ and R₁₆′ are each independently of the other hydrogenor C₁-C₄alkyl that is unsubstituted or substituted by hydroxy or bysulfo, R₁₅ is hydrogen or C₁-C₄alkyl, A is a phenylene radical that isunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen,carboxy or by sulfo or is a C₂-C₆alkylene radical and k is from 1 to 3;

wherein A′ is a phenylene radical that is unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo or is aC₂-C₆alkylene radical, r independently is the number 0, 1 or 2, and vand v′ are each independently of the other the number 0 or 1; or

wherein G is a phenylene radical that is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo or is acyclohexylene, phenylenemethylene or C₂-C₆alkylene radical.
 9. A processaccording to claim 1, wherein the viscosity of the ink is from 6 to 14mPa·s at 25° C.
 10. A process according to claim 2, wherein component(II) is dipropylene glycol or tripropylene glycol.
 11. A processaccording to claim 1, wherein printing is performed by means of anink-jet printing device provided with at least one ink-jet print headwhich comprises a nozzle layer (a) defining a plurality of ejectionnozzles, an ink supply layer (b) which is formed from a porous materialhaving a multitude of small interconnected pores so as to allow passageof ink therethrough, said ink supply layer featuring a plurality ofconnecting bores from the rear surface to the front surface, each ofsaid connecting bores being aligned so as to connect between acorresponding one of said ejection nozzles and a deflection layer (c),comprising a plurality of transducers related to said connecting boresfor ejecting ink droplets out through the nozzles.
 12. A processaccording claim 1, wherein printing is performed by means of an ink-jetprinting device provided with at least one ink-jet print head whichcomprises a nozzle layer (a) defining a plurality of ejection nozzles,an ink supply layer (b) having a front surface associated with thenozzle layer and a rear surface associated with a cavity layer (d), saidink supply layer being formed with a plurality of connecting bores fromsaid rear surface to said front surface, each connecting bore beingaligned so as to connect between a corresponding one of said inkcavities and a corresponding one of said ejection nozzles, wherein saidink supply layer additionally features (i) a pattern of ink distributionchannels formed in said front surface, and (ii) at least one ink inletbore passing from said rear surface to said front surface and configuredso as to be in direct fluid communication with at least part of saidpattern of ink distribution channels, said pattern of ink distributionchannels and said at least one ink inlet bore together defining part ofan ink flow path which passes from said rear surface through said atleast one ink inlet bore to said pattern of ink distribution channels onsaid front surface, and through said porous material to said pluralityof ink cavities. a deflection layer (c), comprising a plurality oftransducers related to said connecting bores for ejecting ink dropletsout through the nozzles.
 13. A process according to claim 1, wherein thetransducer is a piezoelectric element.
 14. A process according to claim1, wherein cellulosic fibre materials are printed.
 15. A processaccording to claim 1, wherein the textile fibre material is pre-treatedwith a liquor comprising a pad dyeing auxiliary comprising a copolymerfrom acrylic acid amide and acrylic acid monomer in an amount of 0.5 to5 g/l of liquor, urea in an amount of 50 to 150 g/l of liquor, a base,in an amount of 20 to 80 g/l of liquor, the sodium salt of anitrobenzene sulfonic acid in an amount of 5 to 50 g/l of liquor, asoftener based on a amino functional siloxane in an amount of 10 to 100g/l of liquor and optionally a salt, in an amount of 50 to 200 g/l ofliquor.
 16. The textile material pre-treated according to claim
 15. 17.An aqueous printing ink for the inkjet printing process, comprising (a)at least one fiber reactive dye of formulaA₁-(Z₁)₁₋₃   ( 1), wherein A₁ is the radical of a monoazo, disazo,polyazo, metal-complexed azo, anthraquinone, phthalocyanine, formazan ordioxazine chromophore having at least one sulfo group, and (Z₁)₁₋₃ is 1to 3 identical or different fiber reactive radicals, or a dye of theformula

wherein Q₁, Q₂, Q₃ and Q₄ are each independently of the others hydrogenor unsubstituted or substituted C₁-C₄alkyl, G₁ und G₂ are halogen, B isan organic bridge member, A₂ and A₃ are each independently of the otheras defined for A₁, or one of A₂ and A₃ is hydrogen or unsubstituted orsubstituted C₁-C₄alkyl, phenyl or naphthyl and the other one of A₂ andA₃ is as defined for A₁, (Z₂)₀₋₁ and (Z₃)₀₋₁ are each independently ofthe other 0 or 1 identical or different fiber reactive radicals, and bis the number 0 or 1; and (b) a di, tri or tetramer of aC₂-C₄-oxyalkylene or a mono- or di-C₁-C₄-alkyl ether of a di, tri ortetramer of a C₂-C₄-oxyalkylene, said ink having a viscosity from 5 to20 mPa s at 25° C.